Polymerizable 5-alkylene-m-dioxanyl acrylic esters



United States Patent 3,267,084 POLYMERIZABLE S-ALKYLENE-m-DIOXANYLACRYLIC ESTERS David Rankin, Kansas City, Kans., and Gerald J. Mantelland Francis R. Galiano, Kansas City, Mo., assignors, by mesneassignments, to Gulf Oil Corporation, Pittsburgh, Pa., a corporation ofPennsylvania No Drawing. Filed May 23, 1962, Ser. No. 196,916

. 38 Claims. (Cl. 260-86.1)

This invention relates to novel acrylic organic compounds. Moreparticularly, it relates to novel acrylate esters having aS-alkylene-m-dioxanyl acrylic ester structure represented by thefollowing formula:

wherein R is hydrogen or a lower alkyl radical (preferably hydrogen ormethyl), R is a lower alkyl radical having one to four carbon atoms or ahydrogen atom, and R and R are selected from the group consisting ofhydrogen, alkyl, and phenyl groups. Also, in the formula n represents aninteger from one to four, inclusive.

When one or both of R and R is an alkyl or phenyl radical, the alkyl orphenyl radical is free of substituents which substantially interferewith the ester exchange reaction by which the S-alkylene-m-dioxanylacrylic esters of this invention are prepared. Permissible R and Rradical substituents can be lower alkoxy such as methoxy, ethoxy,andlike, lower alkyl such as methyl, ethyl, or cycloalkyl, nitro, halosuch as chloro or bromo, dialkylamino such as dirnethylamino and thelike substituents, without departing from the spirit of the herebyprovided invention.

When one or both of R and R is alkyl, alkyl has desirably one to eightcarbon atoms, preferably one to four carbon atoms. The alkyl radical canbe unbranched such as methyl, ethyl, n-octyl, and the like; it can bebranched such as isopropyl, t-butyl, isoamyl, Z-ethylhexyl, and thelike; it can be cyclic such as cyclopentyl, cyclohexyl, cycloheptyl, andthe like; it can be cycloalkyl alkyl such as cyclohexylethyl; or R and Rcan be joined to form a cycloalkyl group in which the carbon occupyingposition 2 in the dioxanyl ring is one of the carbons of the cycloalkylring.

The S-alkylene-m-dioxanyl acrylic esters of this invention are generallyrelatively high boiling liquids which frequently having freezing pointsat about room temperature or below. The acrylates of this invention canbe homopolymerized or copolymerized with another polymerizableethylinically unsaturated compound to form interpolymers. Certain of thepolymers hereby provided from the acrylic dioxanyl esters have theinteresting characteristic of having a desirably high softening point,such as the polymers having groups derived from dioxanyl acrylic esterswherein both R and R radicals are hydrogen.

The acrylic dioxanyl esters of this invention can readily ice beprepared by an ester exchange reaction represented by the followingequation:

wherein ALK represents a suitable alkyl group, preferably methyl orethyl and wherein R R R and n have the definitions set forth above.

The ester exchange reactions by which the compounds of this inventionare provided are conducted at an elevated temperature at which thedesired S-meta-dioxanyl acrylic ester is stable. Ordinarily it has beenfound useful to include in the reaction an ester exchange catalyst suchas an alkyl titanate, e.g., tetrabutyl titanate, or any other usefulester exchange catalyst such as an alkali metal alkoxide, or an alkalimetal oxide, hydride or hydroxide, or the like. The catalysts can beemployed in general in amounts which are catalytic quantities in esterexchange reactions. For example, when tetrabutyl titanate is employed,it has been found suitable to employ about 0.01 to 0.1 mole of thecatalyst per mole of the R R R -substituted dioxanyl alcohol (llII)employed. It is preferable in carrying out the reaction to maintain thereaction temperature above the boiling point of the by-product alcohol(ALKOH) but below the polymerization temperatures of the desiredS-alkylene-m-dioxanyl acrylic ester. It is desired during thepreparation to remove any of the produced by-product alcohol bydistillation, thereby enabling the reaction to go to a greatercompletion, During the reaction it is also highly desired to include inthe reaction mixture a polymerization inhibitor, for example, a tertiarybutylated phenol such as 2,6-ditertiarybutyl-4-methyl phenol,2,6-ditertiarybutyl- 4-methoxy phenol, or the like.

The ester exchange reaction is also preferably, whenever possible,conducted at a high concentration of reactants. Usually it can beconducted in the absence of diluents particularly when theS-hydroxyalkyl dioxanyl intermediate employed (III) is of a low meltingcharacter. However, if desired and if their presence supplements theconversion of the desired acrylic esters, inert reaction solvents can beemployed such as dioxane, toluene, xylene, and the like.

The desired acrylic dioxanyl esters are isolated from the ester exchangereaction mixture by conventional procerudes. For example, a relativelycrude fraction of the desired dioxanyl esters can be obtained from thereaction mixture by fractional distillation. The crude products can befurther purified as by extraction, precipitation, or distillationprocedures of common knowledge to the art. In treating a reactionmixture containing certain catalysts such as tetrabutyl titanate, it isadvisable to destroy residual catalyst activity prior to isolationtreatment. The catalyst activity can readily be destroyed by firstadding to the reaction mixture an inert Water immiscible solvent inwhich the desired ester is soluble, for example, hen-- zene, toluene, orthe like. Then, distilled water is added thereto. The two phase liquidsystem is shaken whereupon the desired acrylic ester is taken up in theorganic phase and removed from the mixture. The organic phase isfiltered and is dried with a suitable drying agent such as anhydroussodium sulfate, and the dried solution of the producedS-alkyle'ne-m-dioxanyl acrylic esters are stripped of solvents. Theproduct residue can be further purified as by fractionally distillingthrough common conventional distillation procedures.

The S-hydroxyalkylene-m-dioxanyl alcohols can be pro vided followingconventional condensation procedures illustrated by the followingreaction:

It is seen that intermediate IV is an appropriately substituted1,3-propane diol.

Intermediate V represents either a ketone or an aldehyde with required Rand R groups. The aldehyde in simplest form will be formaldehyde whereinR and R are both hydrogen substitutents. Other suitable aldehydes arethe following: benzaldehyde, acetaldehyde, chloral, propionaldehyde,isobutyraldehyde, o-, m-, and p-nitrobenzaldehyde, m-chlorobenzaldehyde,anisaldehyde, furfural, and the like. Also, the reactant V can be aketone having R and R groups. Suitable ketones are acetone, methyl ethylketone, acetophenone, cyclohexanone, cyclopentanone, methyl isobutylketone, benzophenone, 3-methylcyclohexanone, and the like.

In carrying on the above described condensation of intermediates 1V andV, in accordance withconventional procedures, it is useful to employ anacid condensation catalyst such as p-toluene sulfonic acid. The reactionis carried out ordinarily at a suitable elevated temperature. Theproduced m-diox'anyl alcohol (VI) is recovered following conventionalprocedures, such as by distillation.

In carrying on any of the above process steps, the preparativetemperatures should be maintained below a point at which neitherpolymerization nor pyrolysis reactions affecting the ring structureoccurs. At times it will be desired to conduct the reactions at loweredpressures in order to avoid the necessity of high temperatures.

The S-m-dioxanyl esters of this invention can be polymerized byfollowing known methods for polymerizing acrylic type monomers.Polymerization can be conducted following bulk, solution, suspension, oremulsion polymerization techniques. Conventional catalysts can beemployed, and are ordinarily advisably used. Such referred toconventional polymerization catalysts include peroxide free-radicalinitiators such as benzoyl peroxide, tertiary butyl hydroperoxide,tertiary butyl perbenzoate, and amtype free-radical catalyst such asalpha, alphaazobis- (isobutyronitrile), alpha, alpha-azobis (ethylisobutyrate) and 2,2-azobis(isobutyramide), and persalts such aspotassium persulfate and the like.

The esters of this invention can also be copolymerized with one or moreethylenically unsaturated monomers polymerizable therewith such as thealkyl esters of acrylic or methacrylic acid such as methyl methacrylate,ethyl acrylate, octyl acrylate and benzyl acrylate; acrylamides such asmethacrylamide; vinyl esters such as vinyl chloride and vinyl acetate;vinylidene chloride; acrylonitrile, allyl compounds such as diallyladipate; vinyl aryl compounds such as styrene and divinyl benzene; andother unsaturated compounds like butadiene and maleic anhydride. It isis to be understood that at times some of the above mentioned monomerswill not polymerize in all concentrations or in all proportions with allof the m-dioxanyl acrylic esters provided by this invention. However,copolymers of this invention can be provided wherein a very small buteffective quantity of one or more of the above m-dioxanyl acrylic estersare incorporated. For example, an effective quanity of an acrylicdioxanyl ester can be as small as about one percent by weight up toabout ninety-nine percent by weight. Preferably, the acrylic dioxanylesters of this invention are contained in the polymers of the order ofat least about two or about ninety percent by weight. It is to beunderstood that the exact concentration will vary depending upon theparticular acrylic dioxanyl ester employed [as well as the otherethylenically unsaturated monomer ormonomers employed.

It is to be further understood that copolymers can be made with amixture of two or more of the novel acrylic dioxanyl esters with orwithout utilization of additional ethylenically unsaturated monomers.

An interesting feature of the polymers of this invention is that theycan be crosslinked as by employing a peroxide free-radical catalyst suchas benzoyl peroxide in the amount of one to two percent by weight basedon the weight of polymer. Elevated curing temperatures are employed suchas a temperature of about C. or greater, preferably temperatures ofabout C. to about 220 C. Also, acid catalysts can be employed such asp-toluene sulfonic acid. It has been found that when p-toluene sulfonicacid is employed to crosslink the polymers of this invention that a ringopening of the dioxanyl rings occurs when the acid catalyzedcrosslinking is conducted in the presence of, e.g., moisture. When theacid catalyzed crosslinking is conducted in substantial absence ofmoisture, an altered mechanism, at times, appears to occur. When R and Rof polymerized ester are methyl groups, acetone apparently is split outon acid curing with moisture, but not is absence of moisture.

Certain agents and certain controls can be usefully employed in thepolymerizations involving the acrylic ester. For example, control oftemperatures and pressures can greatly contribute to the character ofthe end polymer products. Certain agents acting as telogens can beemployed. If emulsion polymerization is employed, emulsifying agentswill be added such as fatty acid soaps, fatty acid esters ofpolyalkylene glycols, sulfated alcohols, or the like.

The polymers provided hereby are useful in coating various objects, asadhesives and are useful in molding and casting operations. For example,the polymer can be ordinarily dissolved in a suitable solvent and laiddown as a cast film. The end polymers can be foamed or they can becrosslinked as by application of heat or by the incorporation of an acidcatalyst or a peroxide catalyst into the polymer mix.

The above provided acrylic dioxanyl esters are additionally highlyuseful in providing a diol of the following formula wherein both of thehydroxy groups of the glycol are primary:

These derivable glycols are disclosed in the copending application filedsimultaneously herewith by Francis R. Galiano et al., Serial Number196,914, now Patent No. 3,210,327. The disclosed glycols can be eitherpolymerized as polyesters such as by the reaction with dicarboxylic acidagents (such as with phthalic anhydride) or can be polymerized throughthe ethylenic unsaturation.

The following examples illustrate the provided invention but are not tobe interpreted as being in limitation thereof except as defined by theappended claims.

Example 1 A solution of 2-hydroxymethyLZ-methyl-1, 3-propanediol (0.25mole, 30 g.) and 37% aqueous formaldehyde (0.25 mole, 20 g.) is acidifedwith p-toluene sulfonic acid hydrate and is heated with stirring foreighteen hours at 85 C. followed by stirring for four and one-half hoursat room temperature. The reaction mixture is then neutralized by theaddition of solid sodium acetate. The neutralized mixture isfractionally distilled in vacuo providing a main fraction containing thedesired dioxane product collected at 72-74" /08 mm. The infraredspectrum of the fraction of 5-hydroxymethyl-S-methyl-mdioxane shows astrong hydroxyl band at 2.8 microns and a strong ether band at 9.1microns in confirmation that the product is the desiredS-hydroxymethyl-S-methylm-dioxane.

Elemental analysis calculated for C H O C, 54.52%; H, 9.15%; found: C,53.98%; H, 8.66%.

Example 2 2-hydroxymethyl-2-methyl-1, 3-propanediol (0.5 mole, 60 g.) ismixed with excess acetone (175 ml.) in a SOO-rnl. flask equipped with aDean-Stark trap and a reflux condenser. A 2:1 mixture by volume of2,2-dirnethylbutane and n-pentane (total vol. 150 ml.) is added to theacetone mixture and the mixture is acidified with 1.5 g. of p-toluenesulfonic acid hydrate. The mixture is refluxed (40 C.) for twenty-ninehours during which time 11 m1. of a water-acetone phase is removed. Thesolution is then neutralized by the addition of anhydrous sodium acetateand is filtered. Solvents are removed by means of a rotating evaporatorand the product is fractionally distilled in vacuo. The main fraction(63 g., 79%) containing the desired dioxane product is obtained at 53-54C./ 0.1 mm. The infrared spectrum of the product shows strong bands at2.8, 9.1, and 12.0 microns which are in confirmation that the product isthe desired 5hydroxymethyl-2,2,5-trimethyl-m-dioxane.

Elemental analysis calculated for C H O C, 59.97%; H, 10.07%; found: C,59.71%; H, 10.04%.

7 Example 3 To a mixture of 206 g. (1.29 moles) ofS-hydroxymethyl-2,2,5-trimethyl-m-dioxane and 440 g. (4.40 moles) ofmethyl methacrylate are added 1.2 g. of 2,6-ditertiarybutyl-4-methylphenol and 29 ml. of tetrabutyl titanate. The reaction flask is attachedto a distillation column consisting of two insulated 12-inch Vigreuxcolumns. Heat is applied and a methyl methacrylate-methylalcohol'azeotrope (85% methanol) boiling at 64565 C. is removedcontinuously over a one and one-half hour period. After 67 ml. ofazeotrope is removed, the temperature rises to 98-100 C. at which point70 ml. of methyl methacrylate is distilled oil. The reaction mixture iscooled and is stripped of excess methyl methacrylate. Benzene (200 ml.)is added to the reaction residue containing the desired dioxane and themixture is shaken vigorously with 40 ml. of water, thereby destroyingthe catalyst activity. The benzene extract is filtered,

is dried over anhydrous sodium sulfate, is stripped of solvents, and isfinally fractionally distilled employing the column describedhereinabove. A fraction of the desired(2,2,5-trimethyl-5-m-dioxanyl)methyl methacrylate is collected (216.5g., 74% at 76-83 C./O.5-1.0 mm.).

Elemental analysis calculated for C H O C, 63.16%; H, 8.77%; found: C,63.29%; H, 9.04%.

Example 4 The procedure of Example 3 is repeated employing an equimolarquantity of 5-hydroxymethyl-5-methyl-mdioxane as the alcohol to providethe corresponding (5- methyl-S-m-dioxanyl)methyl methacrylate having aboiling point of 7273 C./0.5 mm.

Elemental analysis calculated for C H O C, 60.00%; H, 8.00%; found: C,59.76%; H, 8.11%.

Example 5 The procedure of Example 3 is repeated employing equimolarquantities of 5-hydroxymethyl-5-methyl-mdioxane as the alcohol andmethyl acrylate as the acrylic acid intermediate to provide thecorresponding (S-methyl-5-m-dioxanyl)rnethyl acrylate having a boilingpoint of about 57 C./0.2 mm.

Elemental analysis calculated for C H O C, 58.05%; H, 7.57%; found: C,57.81%; H, 7.16%.

Example 6 The procedure of Example 3 is repeated employing an equimolarquantity of methyl acrylate as the acrylic acid intermediate to providethe corresponding (2,2,5-trimethyl-5-m-dioxanyl)methyl acrylate having aboiling point of about 81 C./1.0 mm.

Elemental analysis calculated for C H O C, 61.65%; H, 8.49%; found: C,62.14%; H, 8.95%.

Example 7 CH H orb- Example 8 A bulk polymerization of(2,2,5-trimethyl-5 m-dioxanyl)methyl methacrylate is carried out inglass polymerization oells prepared in the following manner. Two glassplates having the dimensions A" x 4" x 6" Were beveled on one edge.These cells are washed, are dried, and are coated with a 1% solution ofdichlorodimethylsilane in petroleum ether, Igepal CO-630 (a polyethyleneoxide phenol condensation surfactant product sold by General Aniline &Film Company) is then spread on the surface, and is subsequently washedoff thoroughly with distilled Water. After drying, the plates arestacked on top of each other, spaced along the three non-beveled edgeswith moist strips of cellophane. The cell is then sealed on these threeedges with a gelatin-glycerin mixture containing a small amount of waterand is placed in an oven at C. for several hours to harden the seal.

The polymerization is carried out as follows: (2,2,5-trimethyl-S-m-dioxanyl)methyl methacrylate (2.0 g.) is mixed with 2 mg.(0.1%) of 2,2-azoisobutyronitrile as initiator. The material is thenintroduced into the polymerization cell by means of a syringe. When thecell is completely filled, the top edge is sealed with the gelatinmixture and is placed in an oven at 60 C. for eighteen hours. Thematerial then has set and the temperature is raised to C. over atwo-hour period and'kept at that temperature for an additional sixhours. After coolling, the polymer, consisting of homopolymerized(2,2,5- trimethyl-S-m-dioxanyl)methyl methacrylate is removed byscraping off the gelatin seal and separating the plates. The homopolymeris solvent soluble and softens at 115- Following the above procedure(S-methyl-S-m-dioxanyl)methyl acrylate is homopolymerized to provide asolvent insoluble homopolymer.

Example 9 A solution copolymerization of (S-methyl-S-m-dioxanyDmethylmethacrylate and methyl methacrylate is carried out as follows: Benzene(12 ml.) is refluxed under argon for one-half hour in a 100-ml.,three-neck, round bottom flask equipped with a gas inlet, refluxcondenser, syringe cap, and a magnetic stirring bar. Argon is alsobubbled through a mixture of monomers [5 g. of (5-methyl-S-m-dioxanyl)methyl methacrylate and 7.5 g. of methylmethacrylate] for one-half hour at room temperature. The catalyst,2,Z-azobisisobutyronitrile (0.020 g.), is then dissolved in the abovemonomer mixture. The rn0n0 mer-initiator mixture is added dropwise by asyringe to the boiling benzene mixture over a period of one-half hour.After three and one-half hours at reflux, the viscosity of the reactionmixture had increased so that stirring became difiicult. Additionalbenzene (2 ml.) is added to permit stirring. In seven hours after thelast benzene addition, 2 ml. more benzene is added. The reaction mixtureis then heated overnight (sixteen hours) at 50 C. After cooling, 50 ml.of benzene is then added and the reaction mixture is poured into a largeamount of vigorously stirred methanol (1000 ml.). The methanol issuction filtered separating a white solid consisting of the copolymer of(S-methyl-S-m-dioxanyl)methyl methacrylate and methyl methacrylate. Thesolid copolymer is again stirred with 500 ml. of fresh methanol, isfiltered, and is dried under vacuum. The copolymer product is solventsoluble; has the high softening point of 138-165" C and the Barcolhardness value of 90.

Following the above procedure (S-methyl-S-m-dioxanyl)methyl methacrylateis polymerized to form a homopolymer which is soluble in benzene (i.e.,solvent soluble) has an inherent viscosity of 0.99 in tetrahydrofuran at9 25 C. at a concentration of 0.5 g./ 100 ml., softens at 160175 C., andhas a Barcol hardness value of 84.

Following the above procedure (2,2,5-trimethyl--mdioxanyl)methylmethacrylate is polymerized to form a homopolymer which is solventsoluble, oftens at 117- 124 C., has an inherent viscosity of 0.35 intetrahydrofuran at C. at a concentration of 0.5 g./ 100 ml.

Following the above procedure (5-methyl-5-m-dioxanyl)methyl acrylate ispolymerized to form a solvent soluble homopolymer which softens at 6070C., has an inherent viscosity in tetrahydrofuran as above described of0.51, and has a Barcol hardness value of 65 Following the aboveprocedure (2,2,5-trimethyl-5'mdioxanyl) methyl acrylate is polymerizedto form a solvent soluble homoploymer which softens at 4145 C., has aninherent viscosity of 0.62 determined in tetrahydrofuran as describedabove, and has a Barcol hardness value of 65.

Following the polymerization procedures set out in Examples 8 and 9above, the remaining 5-alkylenemdioxanyl esters of Examples 17 can behomopolymerized and copolymerized with copolymerizable ethylenicallyExample 10 In illustration of curing of the polymers of this invention,benzene-soluble, homopolymers of (5-methyl-5-mdioxanyl)methyl and (2,2,5trimethyl 5 m-dioxanyl) methyl acrylates or methacrylates have beencured under the conditions and with the results as described below. Theweights of curing agents are given in percentages by weight based on theweight of the polymer.

A homopolymer of (5-methyl-5-m-dioxanyl)methyl methacrylate cured withone percent by weight of dicumyl peroxide at 146 C. in a dry argonatmosphere after minutes provided a mostly insoluble polymer having apencil hardness value of 5H; at 146 C. after 60 minutes using twopercent by Weight of trichloroacetic acid provided a mostly insolublepolymer having a pencil hardness value of 9H; and at 146 C. after 30minutes using two percent by weight of p-toluene sulfonic acid in amoist argon atmosphere provided a mostly insoluble cured polymer havinga pencil hardness value of 7H. A homopolymer of(S-methyl-S-m-dioxanyl)methyl acrylate cured for 30 minutes at 150 C.using one percent by weight of dicumyl peroxide in the presence of airprovided a cured polymer mostly insoluble having a pencil hardness valueof 5H, and after 90 minutes the cured polymer is essentially completelyinsoluble in benzene and has a pencil hardness value of 9H; using twopercent by weight of trichloroacetic acid in an air atmosphere at 150 C.provided after 30 minutes a mostly insoluble unsaturated monomers, e.g.,acrylonitrile, butadiene, styrene, methyl acrylate, and the like.polymer having a pencil hardness value of 3H, and after 90 minutes acured polymer essentially completely insoluble is provided having apencil hardness value of 6H. A homopolymer of(2,2,5-trimethyl-5-m-dioxanyl)methyl acrylate is cured in an airatmosphere at 150 C. with one percent by weight of dicumyl peroxide toprovide a cured polymer after 30 minutes mostly insoluble and having apencil hardness value of 4H, and after 90 minutes provided anessentially completely insoluble cured polymer having a pencil hardnessvalue in excess of 9H; and with two percent by weight of trichloroaceticacid in an air atmosphere at 150 C. is provided after 30 minutes anessentially completely insoluble cured polymer having a pencil hardnessvalue in excess of 9H.

What is claimed is:

1. A polymerizable S-alkylene-m-dioxanyl acrylic ester represented bythe following formula:

wherein N represents an integer from 1 to 4 inclusive, R is selectedfrom the group consisting of lower alkyl and hydrogen, R is selectedfrom the group consisting of lower alkyl radicals having 1 to 4 carbonatoms and hydrogen, R and R are selected from the group consisting ofhydrogen, alkyl, and phenyl and alkyl and phenyl having attached theretosubstituents selected from the group consisting of lower alkoxy, loweralkyl, cycloalkyl, nitro, chloro, bromo and dialkylamiuo.

2. A polymerizable acrylic ester of claim 1 wherein the ester is anester of acrylic acid.

3. A polymerizable acrylic ester of claim 1 wherein the ester is anester of methacrylic acid.

4. A polymerizable compound of the formula:

5. A polymerizable compound of the formula:

on. CQCHFO 6. A polymerizable compound of the formula:

H -o CH OH2=oH-i 7OoH2o' o C lg CHrO CHs A polymerizable compound of theformula:

0 CH2-O CH3 CHz=O-i J-OCHzC 3H; CH 011 -0 H3 8. A polymerizable compoundof the formula:

CHr-O CH3 H CH2=CHCOCHz-C CH CHz-O A polymerizable compound of theformula:

16. A homopolymer of a compound of claim 1.

17. A homopolymer of a compound of claim 2.

18. A homopolymer of a polymerizable ester claim 3.

19. A claim 4.

20. A claim 5.

21. A claim 6.

22. A claim 7.

23. A claim 8.

24. A claim 9.

25. A claim 10.

26. A claim 11.

27. A homopolymer claim 12.

28. A homopolymer claim 16.

29. A homopolymer claim 14.

30. A homopolymer of the polymerizable claim 15.

31. A copolymer of a compound of claim 1 and an other polymerizab'leethylenically unsaturated monomer of the general formula H C=C 32. Acopolymer of a compound of claim 2 and another homopolymer of thepolymerizable ester of homopolymer of the polymerizable ester ofhomopolymer of the polymerizable ester of homopolymer of thepolymerizable ester of homopolymer of the polymerizable ester ofhomopolymer of the polymerizable ester of homopolymer of thepolymerizable ester of homopolymer of the polymerizable ester of of thepolymerizable ester of of the polymerizable ester of of thepolymerizable ester of ester of 12 polymerizable ethylenieallyunsaturated monomer of the general formula H C=C 33. A copolymer of acompound of claim 3 and another polymerizable ethylenically unsaturatedmonomer of the general formula H C=C 34. A copolymer of the compound ofclaim 5 and methyl methacrylate.

35. A process of providing a crosslinked polymer which comprises heatinga polymer having groups corresponding to a S-alkylene-m-dioxanyl acrylicester of claim 1 with an initiating amount of a peroxide free-radicalinitiator at an elevated curing temperature.

36. A process of providing a erosslin ked polymer which comprisesheating a polymer having groups corresponding to aS-alkylene-rn-dioxanyl ester of claim 1 with an initiating amount of anacid catalyst at an elevated curing temperature.

37. A process of claim 36 wherein the crosslinking is conducted in thepresence of moisture.

38. A process of claim 36 wherein the crosslinking is conducted undersubstantially anhydrous conditions.

References Cited by the Examiner UNITED STATES PATENTS 6/1954 Fegley etal 26086.l 2/ 1960 Pattison 26088.3

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,267,084 August 16, 1966 David Rankin et 211.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 2, lines 52 and 53, for "procerudes" read procedures column 4,line 10, for "or" read to column 6, lines 38 to 41, the left-handprotion of the formula should appear as shown below instead of as in thepatent:

lines 50 to 54, the left-hand portion of the formula should appear asshown below instead of as in the patent:

column 6, lines 65 to 69, the left-hand portion of the formula shouldappear as shown below instead of as in the patent:

column 7, lines 1 to 5, for that portion of the formula reading CH -6read -CH2C 2- 2 (1H2 I 2 CH 2 CH3 lines 6 to 10, for that portion of theformula reading O\C/CH3 read O\C/CH C CH lines 16 to 19, for thatportion of the formula reading CH read -CH CH CH 2 2 -OH -CH2 lines 42and 46, for that portion of the formula reading CH CH -C- 2 read 2 C CHCH CH column 8, line 13, for "ether," read ether. same column 8, lines38 and 72, and column 9, lines 3, 8, and 13, after "procedure", eachoccurrence, insert a comma; column 9, line 15, for "homoploymer" readhomopolymer same column 9, lines 52 and 53, strike out "unsaturatedmonomers, e.g., acrylonitrile, butadiene, styrene, methyl acrylate, andthe like." and insert the same after "ethylenically" in. line 22, samecolumn 9.

Signed and sealed this 5th day of September 1967,

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner ofPatents

1. A POLYMERIZABLE 5-ALKYLENE-M-DIOXANYL ACRYLIC ESTER REPRESENTED BYTHE FOLLOWING FORMULA: